Products from acid sludges



United States Patent 3,470,006 PRODUCTS FROM ACID SLUDGES Henri Brunel,9 Rue du General, Niox, Paris 16, France No Drawing. Continuation-impartof application Ser. No. 181,498, Mar. 19, 1962. This application Oct.21, 1965, Ser. No. 500,169 Claims priority, application France, June 15,1961, 865 052 Int. Cl. C08h 17728,- C04b 34/30 US. Cl. 106-123 ClaimsABSTRACT OF THE DISCLOSURE This application is a continuation-in-part ofmy US. application Ser. No. 181,498, filed Mar. 19, 1962,

This invention relates to a process for obtaining plastic products fromacid sludges and to the products thus obtained.

Among the objects of the invention is to provide a method of obtaininguseful products from acid sludges and similar material which ordinarilyprovide a disposal problem.

Among the objects of the invention is to provide a method of disposingof acid sludges and other Waste products of the petroleum industry whilesimultaneously producing a useful product therefrom.

Among other objects of the invention is to provide a process of makingcompositions such as mastic compositions, useful as waterproofingsealants, coating materials, calking agents and impregnating agents fromwaste materials of the petroleum industry.

The objects of the invention are attained by neutralizing acid sludgesby adding them to a powdered neutralizing agent dispersed in a thickresinous solvent mixture which is liquid at 50-90 C. to directly providethe basic mastic composition of the invention.

The solvent mixture comprises 5-60% of the basic mastic composition andis made up of a mixture of materials selected from the group ofbitumens, higher fatty acids, resinic acids, naphthenic acids, tall oil,with the provision that up to 70% (preferably 5-30%) of the mixture arepreferably natural or synthetic drying oils, unsaturated hydrocarbonextracts obtained in oil refining processes, and unsaturated, dryinghydrocarbon polymers and resins obtained from the preparation of lighthydrocarbon fuels by the steam cracking process and up to 15%(preferably 05-15%) of the mixture is preferably a mineral oil.

The powdered neutralizing agent consists of one or more powderedalkaline earth hydroxides or carbonates. These powdered materials aredispersed in the solvent mixture while maintaining the temperature ofthe latter at 50-90" C. Said neutralizing agents are added in sufficientproportion to neutralize the 20-75% of the acid sludge that is to beadded. This component also reacts with the fatty resinic or naphthenicacids or tall oil to produce corresponding soaps which act asagglutinizing agents.

The acid sludge is added in proportions of 20-75% "ice of the basiccomposition. The metal salts produced by the action of the alkalineearth hydroxides or carbonates with the acid of said sludges act as afiller in the resultant mastic.

Drying agents such as the manganese, iron, lead, cohalt, zinc, calcium,and cerium salts of naphthenic, octoic and decanoic acids may be addedto the composition containing drying oils in the proportion of 0.5 to 5%based on the weight of the composition.

Various additional fillers such as kaolin, mica, clay, fullers earth,infusional earth, calcium sulfate, whiting, metal oxides, cork, sawdust,etc., may be added. As further explained below, spent clay may beincluded as a source of both filler (clay) and solvent (bitumens andother hydrocarbons). Fibrous fillers such as asbestos, rock wool, glassfibers, metal fibers, natural and synthetic organic fibers may be addedfor increasing the strength of the mastic.

Wetting agents may be added for increasing the plasticity andmalleability of the mastic and for aiding in its formation. Suitablewetting agents include the polyalcohols polyepoxyglycols, soaps,sulfonates, amidoalcohol, ester alcohols, etc., and may be incorporatedin proportions of 0.2 to 2% of the composition.

Elastomeric compounds that can be blended with the compositions toprovide compositions which are impenetrable to gas and vapors are thepolybutenes, especially those of relatively high molecular weightbetween 1,500 and 2,500 for example. Also polyvinyl acetates can beblended with the compositions. Epoxide resins and drying esterstherefrom may also be blended with the compositions to providecompositions for very resistant sealing and coatings.

Tars from wood distillation may also be blended with the composition,especially as antiseptics, fungicides and algicide components.

The acid sludges or tars obtained in the refining of mineral oils setforth as a component (a) may further be defined as follows. In therefining of hydrocarbon oils with sulfonating reagents, there isseparated from the refined or reclaimed oil, a dark, pasty or syrupy,strongly acid residue which contains the excess of the sulfonatingreagent (sulfuric acid, etc.) together with compounds resulting from thereaction of this reagent on the unsaturated components of the oil, whichcompounds are insoluble or only partly soluble in the oil phase andsettle at the bottom of the refining tanks in the decantation operationor pass off with the heavier phase in the centrifugal operation. Theseresidues constitute the acid sludges or tars. They may be made up of oneor more of several types of compounds depending on the type of oilrefined, the strength of the sulfonating agent, and the length of timeand temperature of the contact with the sulfonating reagent. Two generaltypes are Water soluble and water insoluble acid sludges.

The water soluble acid sludges which usually are a byproduct of theprocess of highly refining fluid oils utilizing strong sulfonatingreagents, can often be separated and/0r reacted to produce valuableproducts. See applicants French Patent No. 1,251,205, for example.

Water insoluble sludges are produced in greater proportion than thewater soluble type and these products do not have any ready utility andare sometimes discarded in dumps. In fact, however, the disposal of suchsludges has become an industrial problem in many instances. The mostusual method of disposal is by burning which requires ovens and otherequipment made of special materials, etc. My US. Patent No. 3,149,063discloses one process of eliminating or disposing of acid sludges. Anobject of the present invention is to provide another method ofutilizing and simultaneously disposing of said acid sludges (includingthe water insoluble sludges). The fatty acids referred to are the higherfatty acids which may also be obtained from waste materials such asrancid animal and vegetable oils.

The resinic acids are the acids obtained from natural resins.

The naphthenic acids are the acids found in many petroleums.

The drying oils which may be added include the animal, mineral andvegetable drying oils, such as linseed, soya, fish and tall oils, andthe drying mineral oils as defined above.

Another waste product of the oil industry which can be utilizedaccording to the present invention is the spent clay or similar material(fullers earth, for example) obtained as a waste material during thefinal decoloration of refined oil. When the chemical refining of oil isfinished, the oil still is submitted to a decoloring operation byintroducing fullers earth, kieselguhr or bleaching clay or diatomaceousearth into the oil while hot and with agitation and then separating thedecolored oil by filtration. The filter cakes obtained from the filtershave a dark color, having retained some of the hydrocarbons, and presentanother disposal problem. Such waste materials are also useful togetherwith, or in place of the acid sludges described above.

Still other products which present somewhat of a disposal problem arethe drying type of oils produced by the petroleum industry. Such oilsare not adapted for lubricating purposes because of their unstable,unsaturated or aromatic composition. Some such oils are obtained byrefining oils by the solvent extraction method and are known asextracts; other unstable, unsaturated oils are obtained as polymers inthe steam cracking process. These extracts and polymers can be employedfor all or a part of component (a) referred to above.

It has further been found that owing to the diverse uses to which thesecompositions may be put, it is desirable to provide a master batch ofthe basic material.

The present invention also relates to an improved process for preparingthe master batch of the basic material. It had been found that thekneading process for mixing the components of the composition requiresspecial, oversized, corrosion-resistant apparatus because of the gasesand steam liberated during the neutralizing operation. According to thepresent invention a liquid solvent diluting mixture made up of thoseingredients in the mastic (exclusive of the strongly acid sludge) whichare liquid at 50'90 C. is first provided in a suitable mixing vessel,the neutralizing powder is disposed in this liquid mass and onlythereafter are the acid tars or sludges gradually added to this mixturewhile maintaining the temperature thereof at about So -90 C., either byheating, cooling or by adjusting the rate of addition of the acid tars.

In the specification and claims, proportions given are by Weight unlessotherwise specified.

The invention will now be illustrated with Examples of preparationswhich have been realized by the inventor and which shall enable anyoneskilled in the art to perform the process and to obtain the compositionsthereof.

Example 1 In a steel mixer which can be closed and is fitted withaspiration and absorption system for acid vapors, there are introduced140 kilograms of a viscous unsaturated hydrocarbon extract from refiningpetroleum oils by solvent extraction with liquid S phenols, or furfural,having a viscosity not less than 4 Engler at 50 C., for example, theproducts commercially sold under the trademarks Dutrex, Iranolin orNuso, to which are added 80 kilograms of raw tall oil and 80 kilogramsof a hydrocarbon claytreated drying polymer (for instance one of theproducts commercially known under the registered trademarks CTLA Polymer(Clay Treated Louisiana Polymers) or Escopol). To this liquid mixturewhich constitutes the diluting solvent according to the invention, thereare incorporated while mixing 200 kilograms of calcium hydroxide, i.e.,slaked lime. In the homogeneous fluid mixture thus obtained, there areintroduced progressively 350 kilograms of acid sludge obtained in theprocess of rerefining contaminated motor oils with 66 Baum sulfuricacid. The addition of a sludge is effected carefully at the beginning inorder to avoid a sudden and important increase of the temperature withconsequent foaming and swelling of the mass. In case this happens,addition of sludge is immediately stopped until the foam has disappearedand then the addition of sludge is again efiected at suitable speed forobtaining a controlled reaction. In this connection, when the reactionbegins, which is shown by the increase of the temperature, the rate ofaddition of acid sludge is regulated together with the cooling in orderthat the temperature preferably does not overstep the limit of C. andstands at between 60 and 90 C. The quantity of slaked lime has beencalculated to have an excess of neutralizing power with respect to theacid index and the quantity of the acid sludge to enter in the finalcomposition. Said excess of slaked lime acts as saponifying agent forthe tall oil organic acids. There is thus obtained a hot smooth pastewhich constitutes the basic product of the invention and to whichcomplementary products may be added while kneading.

There is now added, kilograms of chalk in fine powder form and 70kilograms of asbestos fiber of medium length. When the paste obtainedafter these additions is homogeneous, and the temperature has decreasedto less than 50 C. there is added 20 kilograms of a drying agent in theform of a solution in white spirit containing lead naphthenate 42%,cobalt naphthenate 12%, manganese naphthenate 14%, white spirit 32%. Thekneading is continued for about one hour and there is finally obtainedan excellent black sealant of low manufacturing cost, having excellenttightness properties, very adherent to any material, remaining palsticafter having been in use for a long time and never becoming brittle.This sealant may be applied with a knife or with a gun and is utilizablefor waterproofing sealing in glazing and roofing and for makingwaterproof joints in the building industry. For applying with gun, theviscosity may be decreased either by adding While manufacturing, 1 to 5%of a spindle petroleum oil or of a synthetic hydrocarbon oil of sameviscosity or by adding in the final composition 1 to 4% of white spiritor benzol.

Example 2 In a steel mixer as in Example 1, there are introducedkilograms of distilled tall oil, 80 kilograms of an unsaturated extractobtained from petroleum refining by solvent extraction having aviscosity of 4 to 6 Engler at 50 C. and 30 kilograms of a synthetichydrocarbon oil of the alkyl aryl type having a viscosity of 4 Engler at50 C. This mixture constitutes the diluting solvent for the acid sludgesaccording to the invention, in which there are incorporated 200kilograms of slaked lime in powder form. In the fluid smooth paste thusobtained there are progressively added while kneading, 300 kilograms ofan acid sludge obtained in refining a lubricating petroleum oil having aviscosity of 8 Engler at 50 C. With 66 Baum sulfuric acid. The perfectlyhomogeneous paste thus obtained, constitutes the basic product accordingto the invention.

To this product, there are added, while continuing kneading, 800kilograms of chalk or calciumv carbonate in powder form, 80 kilograms ofasbestos fiber of medium length, 40 kilograms of asbestos in fine powderform and 20 kilograms of a drying agent consisting of lead, cobalt, andmanganese naphthenate dissolved in white spirit. Kneading is continueduntil homogeneous. Thereafter, 10 to 20 kilograms of white spirit may beadded for obtaining a viscosity suitable for applying with a spatula,hand gun or air gun. The brown paste constituting the final compositionthus obtained, may be used as a mastic or putty since it is veryadherent, remains plastic even after having been exposed for a long timeand never becomes brittle. It is suitable for sealing in the buildingindustry and especially for glazing.

Example 3 The sludges from re-refining with 66 Baum sulfuric acid ofcontaminated motor oil of Example 1 or the sludges from refining,lubricating petroleum oil of Example 2, are replaced by acid sludgescoming from super refining or an oil of a viscosity of 5 to 7 Engler at50 C., having first been refined by solvent extraction with furfural andthen further or super refined with oleum to prepare viscouspharmaceutical oils of a viscosity of about 5 Engler at 50 C., asrequired by pharmacopoeia specifications. The treatment is the same asin Examples 1 and 2, but the proportion of neutralizing agent (slakedlime in powder form) is adapted to the acid content of the sludge asdetermined by simple analysis. In this connection, it is emphasized thatthe acid content of this sludge is variable according to the step ofrefining from which the acid sludge comes, since super refining witholeum is frequently effected in several steps using difierentproportions of acid reagent (see applicants Patent No. 3,164,547).

Sludges coming from the last refining steps are of little interest forthe present process on account of their very high excess of sulfuricreagent. Such last step acid sludges are often used in refineries as asulfonating reagent for former steps or for other refining operations,precisely on account of their high content in sulfuric reagent. However,in the refineries effecting oil super refining, the sludges which arenot reused as sulfonating reagent are discarded altogether and thesesludges which are ordinarily discarded are the sludges which are treatedaccording to the present invention. Nevertheless, it is emphasized thatwhere the process of this application is to be exploited on a largescale it is preferable to use fresh sludges coming from a determinedstep of refining or mixtures of sludges from different steps but alwaysin about the same proportion when it is desired to obtain uniformproperties for the compositions of the process obtained from such acidsludges. It must be noted, besides, that the sealants obtained with theacid sludges from the super-refining of oils as in the present example,are usually not of black color but of a more or less clear brown color.

Example 4 140 kilograms of petroleum bitumen having a melting pointbetween 95 and 120 C. are molten or introduced in the liquid state in aheated mixer of the type described in Example 1. Then, there are addedin the liquid bitumen 150 kilograms of raw tall oil, 60 kilograms of thesame unsaturated extract as in Example 1, 70 kilograms of the samehydrocarbon drying polymer and 30 kilograms of a synthetic hydrocarbonoil of the alkyl aryl type having a viscosity of 3 to 4 Engler at 50 C.or the corresponding amount of a spindle petroleum oil preferably of thenaphthenic type. While mixing, there is formed a liquid mixture of whichthe temperatureis maintained between 50 and 90 C. In this mixture thereare introduced, while kneading, 100 kilograms of slaked lime in powderform and in the fluid, smooth paste thus obtained, 250 kilograms of acidsludges of the same type as in Example 1 are introduced progressivelywhile kneading and regulating the temperature within the same range of60 90 C.

To the homogeneous basic pasty product thus obtained according to theprocess of the invention, complementary products are added as follows:140 kilograms of chalk in powder form and 60 kilograms of asbestos fiberof medium length. Finally, there are incorporated, when the temperaturehas decreased under 50 C., 20 kilograms of the same drying agent as inExample 1 and there is obtained an excellent black sealant especiallysuitable for waterproofing, the sealing of glass, the sealing of cracksand sealing of intervals between parts of building foundations.

Example 5 With a view of increasing adhesive and drying properties, talloil is replaced in Examples 1 to 4 by an oil selected from linseed oil,soya oil, fish oil which may be partly mixed with olein and in whichthere is dissolved an abietic resin or a resinic polymer from steamcracking.

Example 6 In Examples 1 to 4, tall oil is replaced by an additionalamount of the clay-treated drying polymer (sold under the trademark CTLA(Polymer or Escopol). The drying properties of the resultant mass, thesuperficial waterproofing properties of the dry film formed on thesurface thereof when applied, is thereby increased and the resultantcomposition is free of vegetable or animal oils which are fermentablewhen in presence of humidity and water.

Example 7 300 kilograms of spent clay of light grey color, extractedfrom filter plates employed in the decoloration of a whitepharmaceutical oil of a viscosity between 4", 5 and 6 Engler at 50 C.are progressively mixed with a diluting solvent consisting of 40kilograms of tall oil, 40 kilograms of the unsaturated hydrocarbonextract sold under the trademark Iranolin and 4-0 kilograms ofhydrocarbon drying polymer sold under the trademark of CTLA Polymer,while heating and kneading at between 50 and C. The homogeneous pasteobtained constitutes the basic composition of the invention.

To this composition, there are added, while hot and while keading, 500kilograms of chalk in powder form and 50 kilograms af asbestos fiber ofmedium length. 20 kilograms of the drying agent as in the above examplesare then added when the mass has cooled under 50 C. There is obtained amastic of light grey color which rapidly congeals and is suitable forglazing and sealing.

Example 8 430 kilograms of black spent clay extracted from filter platesin decoloration of a re-refined motor oil which has been treatedaccording to the conventional process of regenerating contaminated motoroil with 66 Baum sulfuric acid, are mixed with a diluting solventcomprising 250 kilograms of molten high vacuum petroleum bitumen, or airblown petroleum bitumen of melting point about 140-160 C. mixed with 70kilograms of the unsaturated hydrocarbon extract sold under thetrademark Dutrex V4.

To the hot, fluid, homogeneous paste thus obtained, constituting thebasic composition of the invention, there are added, while keadingkilograms of calcium carbonate, 80 kilograms of asbestos fiber of mediumlength and, finally, when the temperature has decreased under 50 C., 20kilograms of the drying agent described in Example 1. There is obtainedan excellent black mastic suitable for glazing and sealing in thebuilding industry and of which the viscosity may be adapted to the meansfor applying by adding a supplement of Dutrex V4, or 5 to 30 kilogramsof white spirit or benzol at the end of the preparation.

Example 9 In Example 8, the 70 kilograms of Dutrex V4 are replaced by 25kilograms of linseed oil, 25 kilograms of tall oil and 25 kilograms ofDutrex V4.

Example 10 "in Example 8, the proportion of spent clay is reduced to 350kilograms and the proportion of bitumen increased to 350 kilograms inorder to increase the waterproofing properties of the completecomposition. There may be also added from 10 to 60 kilograms of a lighthydrocarbon oil in the diluting solvent of the present example forobtaining the viscosity desired.

Example 1 1 In a heated mixer of Example 1, there are molten 100kilograms of bitumen having a melting point of 95-150 C. which may havebeen derived from coal, shale or petroleum. Into the molten bitumen,there are mixed 70 kilograms of raw tall oil, and 70 kilograms of theunsaturated hydrocarbon extract sold under the trademark Iranolin 80. Tothe diluting solvent thus obtained, there are incorporated 100 kilogramsof spent clay from decoloration of a re-refined motor oil and 150kilograms of slaked lime in powder form. To the fluid hot paste, thusobtained there are added progressively, while kneading, 250 kilograms ofan acid sludge from re-refining of contaminated motor oil With 66 Baumsulfuric acid as in Example 1.

To the basic composition thus obtained, there are added while kneading,100 kilograms of chalk in powder form, 70 kilograms of asbestos fiber ofmedium length and, when temperature has decreased to below 50 C.,kilograms of the white spirit solution of the same drying agent as inExample 1 mixed with 70 kilograms of the hydrocarbon drying powder soldunder the trademark CTLA Polymer. There is thus obtained, an excellentsealant containing both acid sludge and spent clay suitable for manysealing applications in the building industry.

Example 12 In a mixer as in Example 1, there are molten 270 kilograms ofpetroleum bitumen with which there are mixed 40 kilograms of unsaturatedhydrocarbon extract sold under the trademark Dutrex V4, and 40 kilogramsof fluid synthetic hydrocarbon oil of the alkyl aryl type having aviscosity of about 2 Engler at 50 C. To the diluting solvent thusobtained, there are added, Whlle mixing, 380 kilograms of spent clayfrom decoloration of re-refined motor oil and then 40 kilograms of thehydrocarbon drying polymer sold under the trademark CTLA Polymer.

To the basic composition thus obtained, there are added, while kneading,50 kilograms of chalk in powder form and 70 kilograms of asbestos fiberof medium length, as fillers, and as special complementary waterproofingand water-repellent product, 90 kilograms of a fatty alkylaminopropylamine salt of naphthenic acid, of which the fatty alkyl aminogroup is derived from tallow and in which the alkyl radical has, thus,from 8 to 18 carbon atoms. Finally, there is added as a drying agent 20kilograms of the white spirit solution of metal naphthenates as inExample 1, and, optionally, for obtaming suitable viscosity, 1 to 3% ofwhite spirit or benzol. There is obtained a black sealant havingwaterproofing properties capable of forming a very water-repellent filmand adapted for sealing under water.

Example 13 For obtaining a product for coating having the samewaterproofing properties and being useful for the protection of metalsagainst corrosion, the 70 kilograms of asbestos fiber of Example 12 arereplaced by 70 kilograms of asbestos in fine powder form or the sameamount of silica or of talc. Then the proportion of the light solventfinally added is increased in order to obtain the desired fluidity topermit application in layers of the desired thickness. Said solvent maybe white spirit or light gasoline, or benzol, or a volatile ketone suchas methylethyl ketone or a chlorinated hydrocarbon solvent such astrichlorethylene.

Example 14 When a composition for the protection of metal surfacesagainst corrosion is desired a filler able to act as a chemicalinhibitor of corrosion is incorporated in the composition of Examples 12or 13, thus zinc chromate in powder form may be added in proportion of 3to 10% to said compositions.

Example 15 The fluidified composition of Example 13, is brought to thesuitable viscosity for painting, spraying or dipping With a view tocoating surfaces with thin films, by diluting with a light solventselected from light hydrocarbon solvents, benzols, volatile chlorinatedsolvents, volatile ketones and is submitted to grinding in a paintgrinder for obtaining an extremely fine dispersion of the fillers in theliquid midst so as to prevent decantation when the product settlesduring storage. Anti-precipitating paints stabilizers may be also addedwith this end in view, for instance, amine phosphates. Othercompositions of the above examples when diluted with solvents and whilereplacing fibrous fillers by pulverulent fillers may be treated the sameway and for the same purpose, especially compositions of Examples 1 and16.

Example 16 In Examples l-ll and 13-15, there are added as in Example 12to the components set forth, 3 to 10% of a fatty amine or polyaminenaphthenate for the same purpose of securing highly waterproofingproperties and for allowing sealing or coating under water.

Example 17 In a heated mixer preferably closed and fitted withaspiration and absorption system, there are molten 350 kilograms of apetroleum bitumen having a melting point of 100150 C. In the moltenbitumen, there are mixed 100 kilograms of the viscous unsaturatedextract from petroleum oil refining by solvent extraction known underthe registered trademark Iranolin 80. Then there are incorporated inthis hot fluid mixture constituting the diluting solvent 200 kilogramsof slaked lime in powder form. The temperature having decreased to about0, there are progressively introduced in the smooth paste thus formed,350 kilograms of an acid sludge from rerefining of contaminated motoroil with 66 Baum sulfuric acid. There is obtained a homogeneous, brightblack mass having the consistency of a fluid paste when hot and which,after cooling, forms a compact solid mass constituting a very importantbasic composition. This composition is, in fact, possessed with highadhesive and very interesting plastic properties allowing it to be usedfor ground and roadways coating, either as it is or by mixing withgranulous fillers of desired size. It may also be supplemented by theaddition of very diverse complementary products with a view to obtainingcompositions for specialized applications. For instance by adding dryingoils, fillers and drying agents for obtaining sealants of the typestated in Example 1 which can be applied with knife or hand or air gun;or by adding both drying oils, pulverulent fillers, volatile solventsand drying agents as in several of the above examples, for obtainingfluid coatings and paints, or by adding water-repellent products as inExamples 1215. In a mixture with spent clay in proportion of 20 to thereis obtained a very cheap and very interesting product for Waterproofbinding of materials in public works applications, especially fordamming of waters.

Example 18 To 100 kilograms of the basic composition obtained inExamples 1 or 17, there are mixed 50 to 250 kilograms of the CTLAPolymer or Escopol defined hereabove for obtaining core oils of aviscosity allowing easy mixing with siliceous sand to provide a good andfilm agglomeration adaptable for preparing molds for metal molding inmetallurgy. After baking, cores are obtained having very good mechanicalresistance.

Example 19 In Example 18, there are mixed with CTLA Polymer or Escopol,20, to 200% of linseed oil, or of fish oil or of a mixture of both fishoil and linseed oil.

Example 20 In Example 18 there is used instead of CTLA Polymer orEscopol a soltltlOn in linseed oil or in fish oil of a resinic polymerfrom unsaturated light hydrocarbons obtained in stream-cracking, forinstance of the resin commercially known under the registered trademarkEscorez.

Example 21 In the Examples 1 to 17, which relate to obtaining sealants,there are mixed with the compositions set forth, polybutenes of highmolecular weight, between 1500 and 2500 in proportion between 2 and 40%depending on the application desired. There are obtained waterproofingsealants providing liquid, gas and vapors tightness and utilizable fortight sealing in any atmosphere and under water.

Example 22 Before adding fillers to the basic compositions obtained inthe above examples, from acid sludges, said compositions are diluted soas to obtain a relatively low viscosity liquid by adding a light solventsuch as light gasoline, white spirit, benzol, dichlorethane,trichlorethylene, perchlorethylene, methyl-ethyl ketone, methyl-isobutylketone, acetone, the solvent being chosen or several solvents beingcombined for obtaining the best solubility for the product obtained fromthe acid sludge. Such diluted solutions are useful for providing thinprotective coatings on surfaces to be protected or, when very fluid, forimpregnation of materials with a view to preservation and waterproofing.In this case, special additions, as for the sealants, may be effected,for instance additions of water-repellent drying fatty amine salts andas drying agents, metal naphthenates or octoates and decanates. Creosotemay be also added. The coatings or impregnations effected with thediluted solutions have shown bactericide and fungicide properties whichhave interesting applications in the protection against putrificationsof the materials coated or impregnated with these solutions. Thesolutions for impregnation may be filtered and the sediment recoveredused in compact compositions.

Example 23 In Example 17, the 200 kilograms of slaked lime are partlyreplaced by a concentrated aqueous solution of an alkali-metal base, inproportion of to 50% which are added after the slaked lime forcompleting the neutralization. There is obtained a composition which, inthe liquid state may be emulsified by agitation with hot water to givestable emulsions when cooled. Such emulsions are suitable for coatingwithout requiring solvents.

Example 24 To 100 kilograms of the composition obtained in Example 1,there are added 10 to 50 kilograms of a solution of polyvinyl acetate inmethylcyclohexanone or in diacetone alcohol of a concentration between25 and 40%. There are thus obtained sealants and products for coatinghaving a certain elasticity and good mechanical resistance.

Example 25 100 kilograms of the composition obtained in Example 1 or inExample 17 are kneaded with 50 to 100 kilograms of a 50% concentrationpolyvinyl acetate aqueous emulsion plastified With butylphtalate. Thehomogeneous composition thus obtained constitutes an excellent sealantwhich is very adherent, elastic, and mechanically resistant.

Example 26 The aqueous emulsion or the solution of polyvinyl ace tateused in Examples 24 and 25 are introduced in proportion of 10 to 50% ascomponents of the diluting solvent in the manufacturing of compositionsaccording to the invention set forth in the above Examples.

Example 27 Instead of the white fillers set forth in above examples,colored fillers may be used for obtaining colored compositions accordingto the process of the invention. For instance, for obtaining redsealants or paints, iron oxide is added as a filler in proportion of 2to 25%. Metal powders and especially aluminum powder may also be addedas fillers for giving a metallic aspect to the sealants, coatings orpaints described in the above Examples, and for increasing theirwaterproofing, protective and tightness properties. In the case of lightcoatings to be applied to light materials, for instance forsound-proofing, fillers of the organic type such as for instancecellulose powder, wood flour, cork powder may be incorporated in thecompositions of the invention instead or in combination wit-h mineralfillers.

Now it must be understood that acid sludges are a rough residue of whichthe composition may vary within important limits as to oil and inorganicacids retained and to organic compounds content, so that, in all theabove examples, the proportions of the components may vary according tothe origin of the sludge, that is to say more precisely, according tothe oil which has been refined and to the details of the method forrefining. Neverthless, anyone skilled in the art will be able to adaptwithout difficulty the formulations of the above examples to thecomposition of the sludge he has to employ. The principal corrections toeffect will concern the proportion of the diluting solvent for the acidsludges, of neutralizing agent and of fillers in order to obtain thefinal product in the form suitable for the application desired. Anyhow,and despite these possibile variations, of proportions of the components, the process and the compositions of the invention do not changeand remain realizable according to the method and formulations hereabovestated and described. The inventor has checked the various examples withspecimens of acid sludges and spent clays supplied to him by differentimportant refineries situated in different countries of the world,especially in France, United States, England, Germany and Spain.

I claim:

1. In the process of forming a mastic suitable as a sealing and coatingmaterial comprising acid sludge as an essential ingredient thereof thesteps comprising (a) providing 5-60% of a solvent mixture which isliquid at 50-90 C. consisting essentially of the following ingredients,

(1) a basis material selected from the group consisting of bitumens,higher fatty acids, resinic acids, naphthenic acids, tall oil, andmixtures thereof,

(2) from 5 to 70% of said solvent mixture being a material selected fromthe group consisting of drying oils, unsaturated hydrocarbon extractshaving a viscosity of not less than 4 Engler at 50 C., obtained from oilrefining processes, and unsaturated drying hydrocarbon resins obtainedin the preparation of light hydrocarbon fuels and in the steam crackingprocess,

(3) up to 15% of said solvent mixture consisting of a mineral oil,

(b) dispersing a powdered neutralizing agent selected from the groupconsisting of alkaline earth metal hydroxides and carbonates in saidsolvent mixture while maintaining the temperature thereof at about 50-90C.,

(c) thereafter gradually adding 20-75% of an acid sludge thereto,

the proportion of neutralizing agent added being sufficient toneutralize all of said acid sludge whereby to provide a basic masticcomposition containing alkaline earth metal salts as a filler.

2. The process as claimed in claim 1 comprising adding 0.5 to of dryingagent selected from the group consisting of manganese, iron, lead,cobalt, zinc, calcium and cerium salts of naphthenic, octoic anddecanoic acids to the composition after the sludge addition has beencompleted.

3. A sealing and coating composition comprising a base material made upof 5-45% of a solvent mixture which is liquid at 50 C.90 C. andconsisting essentially of (1) a basis material selected from the groupconsisting of bitumens, higher fatty acids, resinic acids, naphthenicacids, tall oils, and mixtures thereof, (2) 570% of a material selectedfrom the group consisting of drying oils, unsaturated hydrocarbonextracts having a viscosity of not less than 4 Engler at 50 C. obtainedfrom oil refining processes, and unsaturated drying hydrocarbon resinsand (3) up to of a mineral oil and 75% of the reaction product of anacid sludge with a compound selected from the group consisting of alkaliearth metal hydroxides and carbonates.

4. A process as claimed in claim 1 in which a portion of unsaturatedhydrocarbon solvents is added to the solvent mixture in the form ofspent clay containing such hydrocarbon residues.

5. A sealing and coating composition as claimed in claim 3 wherein saidsolvent mixture contains 545% of said component (2) and comprising 0.5to 5% of a drying agent.

6. A sealing and coating composition comprising 10 to 90% of the basematerial of claim 3 and containing in addition:

0.5 to 5% of a drying agent,

2 to of a fibrous filler based on the total amount of the finalcomposition.

7. A sealing and coating composition comprising 10- 90% of the basematerial of claim 5 and containing additional 'pulverulent fillermaterial to provide up to 40% of total filler based on the total amountof the final composition.

8. A coating composition comprising l090% of the base material of claim5 and containing 1 to based on the weight of the final composition of avolatile solvent, said volatile solvent being present in sufficientproportion to provide a composition which is fiowable at normal roomtemperatures.

9. A sealing and coating composition comprising 10 of the base materialof claim 5 and comprising in addition 0.2 to 2% based on the totalweight of the final composition of a wetting agent.

10. A sealing and coating composition comprising 10- 90% of the basematerial of claim 5 and comprising a significant proportion of asolution of polyvinyl acetate.

11. A sealing and coating composition as claimed in claim 5 comprising3-10% of a fatty alkylamino propylamine salt of naphthenic acid of whichthe alkyl group thereof contains 8 to 18 carbon atoms to provide waterrepellency.

References Cited DONALD J. ARNOLD, Primary Examiner US. Cl. X.R.

